CN107722241B - A kind of epoxy hardener and its preparation method and application - Google Patents
A kind of epoxy hardener and its preparation method and application Download PDFInfo
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- CN107722241B CN107722241B CN201711019516.0A CN201711019516A CN107722241B CN 107722241 B CN107722241 B CN 107722241B CN 201711019516 A CN201711019516 A CN 201711019516A CN 107722241 B CN107722241 B CN 107722241B
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- component
- compound
- epoxy resin
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 47
- 239000004848 polyfunctional curative Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003822 epoxy resin Substances 0.000 claims abstract description 70
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 70
- -1 mercaptan compound Chemical class 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004567 concrete Substances 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002989 phenols Chemical class 0.000 claims abstract description 16
- 230000008439 repair process Effects 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000003973 paint Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 8
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 238000010792 warming Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims description 10
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 8
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- MJQWABQELVFQJL-UHFFFAOYSA-N 3-Mercapto-2-butanol Chemical compound CC(O)C(C)S MJQWABQELVFQJL-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 2
- 239000005711 Benzoic acid Substances 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003512 tertiary amines Chemical class 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 21
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000002118 epoxides Chemical class 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 4
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 229920006334 epoxy coating Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000013035 low temperature curing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- YAGBAUUBKBTRNY-UHFFFAOYSA-N CO[SiH](OC)OC.C(C=C)(=O)OCCC[SiH2]OCC Chemical compound CO[SiH](OC)OC.C(C=C)(=O)OCCC[SiH2]OCC YAGBAUUBKBTRNY-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- LKFAPHHHWRMPGC-UHFFFAOYSA-N butan-1-ol prop-2-enoic acid Chemical compound CCCCO.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C LKFAPHHHWRMPGC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of concrete repair paint epoxy hardeners and its preparation method and application.The preparation method of the epoxy hardener include: 1) phenolic compound containing carboxyl sulfhydrylation phenolic compound is reacted to obtain with mercaptan compound；2) under the action of acidic catalyst, aminated compounds, sulfhydrylation phenolic compound and aldehyde compound are uniformly mixed, react to obtain sulfydryl sealing end phenolic aldehyde amine；3) it is passed through ammonia into the mixture of chlorination titanium compound and benzene, the pH value to reaction system reaches 9~10, is slowly added to sulfydryl sealing end phenolic aldehyde amine, distills to obtain epoxy hardener of the present invention after reaction.Epoxy hardener of the present invention can be mixed with epoxy resin, prepare concrete repair paint composition epoxy resin.Sulfydryl, tertiary amine and phenolic hydroxyl group present in curing agent molecular structure of the present invention have collaboration facilitation, can have good caking property to concrete material in -25 DEG C or less cured epoxy resins.
Description
Technical field
The invention belongs to epoxy resin fields, are specifically related to a kind of concrete repair paint low temperature and high relative humidity epoxy hardener
And preparation method thereof and its purposes for being used to prepare concrete repair paint composition epoxy resin.
Background technique
Epoxy resin has excellent mechanical property, ageing-resistant performance, water resistance, resistant to chemical media and good acid resistance
Can, since epoxy resin has the above performance advantage, occupies an important position it in synthetic adhesive, now use both at home and abroad
It reinforces in adhesive products, 90% or more belongs to epoxy type adhesive, or even requirement must use ring in certain reinforcings specification
Oxygen type adhesive.
Civil construction is complicated system engineering, and by constructing, a variety of effects such as bad, sleet erosion, environment temperature are influenced
Off-seam and crack can be generated, if repaired not in time, under the action of various deterioration factors, crack and off-seam can constantly expand
Exhibition and aggravation, bring very big security risk and economic loss.
Mainly whether there is or not machine patching material, organic/inorganic composite material and organic polymers to repair material for concrete repairing material
Material, organic polymer patching material solve the problems, such as that inorganic patching material adhesion strength is low, cubical contraction is big, improve tree
Adhesion strength and flexibility between rouge and substrate are a kind of patching materials of excellent combination property.
Common organic polymer patching material includes acrylic resin, polyurethane and epoxy resin, acrylate
There is a problem of that the early period lower and mobility of intensity is poor；Its curing time of polyurethane repair material is long, viscosity is high, shrinks deformation
Big and mechanical strength is low, is difficult to meet requirement of the bridge repairing technique to material.
Epoxy resin can be formed and be handed over curing agent under proper condition containing more than two epoxy groups in a molecule
The general name of networking shape solidfied material, the common curing agent of epoxy resin have anhydride, amine and synthetic resin.Currently on the market
Concrete repair paint it is generally in the majority with room temperature slow curing type, when environment temperature is lower than 10 DEG C, film formation reaction speed is slowly and cannot
Sufficiently reaction, for especially environment temperature at 0 DEG C or less, common amine curing agent and epoxy resin are difficult film-forming, in north
Square winter environment temperature often maintains -10 DEG C or so, since environment temperature is too low to delay duration of antiseptic project, by
This is as it can be seen that the low temperature curing properties of existing epoxy coating have been unable to meet actual needs.
US4092293 causes Polymerization of Propylene Oxide, with allyl capped, then and H using pentaerythrite as initiator2S reaction
A kind of Polymercaptan curing agent under cryogenic conditions is obtained, but the shortcomings that preparation method is that reaction step is lengthy and tedious, condition
Harshness, cost of material is more expensive, at high cost.
CN102391476A uses sorbierite/thioacetic acid/p-methyl benzenesulfonic acid/toluene, is prepared for gathering by esterification
Polythiol hardener, each molecule possesses 8~12 mercaptos after Epoxy resin chain extension, good with the compatibility of epoxy resin, but
It is that the curing agent is short compared with the hybrid manipulation time of epoxy resin, is unsatisfactory for the requirement of large-scale casting and constructing.
CN106318302A discloses 3- sulfydryl acrylate (TMOMP) as the promotion of dicyandiamide/epoxy curing systems
Agent can significantly shorten the curing time of epoxy resin adhesive and reduce solidification temperature, still, polymercaptan curing accelerator dosage
Must be appropriate, because not only resulting in curing time extension, and will lead to epoxy resin adhesive performance when dosage is excessive
It reduces.
CN102604044A discloses a kind of thiourea modified low temperature curing agent and preparation method thereof, and reactivity is high, can
It is fully cured, but the solidfied material toughness after being fully cured with epoxy resin is poor, can not be used as tensile materials in winter.
In view of the above-mentioned problems, needing to provide a kind of concrete epoxy resin mending paint, which can not only be in low temperature
The solidification of super-humid conditions lower short time, and solidfied material has excellent mechanical property and corrosion resistance, repairs to meet concrete
The use of benefit.
Summary of the invention
One of the objects of the present invention is to provide a kind of epoxy hardener, the epoxy hardener can be used for preparing coagulation
Native mending paint composition epoxy resin.
To achieve the above object, the technical solution adopted in the present invention is as follows:
A kind of concrete repair paint epoxy hardener, the epoxy hardener are mercaptan modified titanate esters phenolic aldehyde amine,
Structural formula is as follows:
Wherein, R1It representsR2It represents R3It representsR4It representsN is 1 or 10~100, and m is 3 or 4.
The present invention also provides the methods for preparing the epoxy hardener, comprising the following steps:
1) be 1:(1.01~1.05 according to molar ratio by the phenolic compound containing carboxyl and mercaptan compound), preferably 1:
(1.02~1.04) after reacting 2~5h, preferably 3~3.5h, remove water under the conditions of 160~180 DEG C, preferably 165~175 DEG C
Point, obtain sulfhydrylation phenolic compound.
2) it is 1:(0.5~3 by molar ratio under the action of acidic catalyst): (0.5~6), preferably
1:(0.6~2.7): aminated compounds, sulfhydrylation phenolic compound and the aldehyde compound mixing of (0.6~5.5)
Uniformly, 80~120 DEG C, preferably 90~115 DEG C are warming up to, 7~15h, preferably 9~14h is reacted, is cooled to room temperature, obtains sulfydryl envelope
Hold phenolic aldehyde amine.
3) chlorination titanium compound is added in benzene under agitation, 15 DEG C is cooled to after addition hereinafter, logical
Enter ammonia, the pH value to reaction system reaches 9~10, is slowly added to sulfydryl sealing end phenolic aldehyde amine, is warming up to 40~90 DEG C, preferably 55
~85 DEG C, 3~7h, preferably 3.5~6h are reacted, is distilled after reaction, collection absolute pressure is 0.02~0.2MPa, preferably
0.09~0.1MPa, temperature are the fraction of 120~155 DEG C, preferably 130~140 DEG C, obtain epoxy hardener of the present invention.
Phenolic compound described in step 1) of the present invention containing carboxyl is in m-hydroxybenzoic acid and P-hydroxybenzoic acid
One or two, preferred P-hydroxybenzoic acid.
Mercaptan compound described in step 1) of the present invention is 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 4- sulfydryl-n-butyl alcohol
With one of 2- sulfydryl -3- butanol or a variety of, preferably 2 mercapto ethanol.
Acidic catalyst described in step 2) of the present invention is selected from the hydrochloride of acetic acid, hydrochloric acid and amine, the hydrochloride of the amine
It is preferred that dimethylamine hydrochloride；The more preferable acetic acid of acidic catalyst.
The dosage of the step 2) acidic catalyst of the present invention is 0.01mol%~0.1mol% of aminated compounds.
Aminated compounds described in step 2) of the present invention is the double secondary amine of aromatic series, such as WANALINK6200 of ten thousand China's chemistry,
One of UNILINK7100, UNILINK4100 and UNILINK4102 of air chemical industry or a variety of, preferably ten thousand China's chemistry
WANALINK6200。
Aldehyde compound described in step 2) of the present invention is in the formalin and paraformaldehyde of 35wt%~40wt%
One or two, preferred paraformaldehyde, the paraformaldehyde (CH2O) n, n are 10~100.
Chlorination titanium compound described in step 3) of the present invention be one or both of titanium trichloride and titanium tetrachloride, it is excellent
Select titanium tetrachloride.
The molar ratio of chlorination titanium compound of the present invention and sulfydryl sealing end phenolic aldehyde amine is 1:3~4.05.
The dosage of the step 3) benzene of the present invention is for 10mol%~50mol% of chlorination titanium compound.
Epoxy hardener of the invention or epoxy hardener prepared according to the methods of the invention can be used for and asphalt mixtures modified by epoxy resin
Rouge mixing, prepares the composition epoxy resin as concrete repair paint.
A kind of concrete repair paint composition epoxy resin includes following components:
Component A: epoxy resin host agent；With
B component: the curing agent mixture comprising epoxy hardener of the present invention.
In composition epoxy resin of the present invention, the mass ratio of component A and B component is (3~8): 1, preferably (3.5~
7):1。
Component A of the present invention is prepared by the raw material comprising following components, is based on component A weight:
60.0~80wt% of epoxy resin；Preferably 70~78wt%；
2~20wt% of diluent；Preferably 7~15wt%；
1~20wt% of defoaming agent, preferably 8~15wt%.
B component of the present invention is prepared by the raw material comprising following components, is based on B component weight:
85~97wt% of epoxy hardener
3~15wt% of coupling agent
Epoxy resin in component A of the present invention is one of bisphenol A-type and bisphenol f type epoxy resin or a variety of；
It is preferred that epoxide number is 0.1~0.65, is at room temperature one of bisphenol A-type and bisphenol f type epoxy resin of liquid or a variety of；More
It is preferred that epoxide number is 0.4~0.55, is at room temperature the bisphenol A type epoxy resin of liquid.Including but not limited to Shanghai Resin Factory
One of E-44, E-51 and E-54 etc. or a variety of.
Diluent in component A of the present invention is one of reactive diluent and non-activated thinner or a variety of；It is excellent
The diluent of choosing contains C12-C14 alkyl glycidyl ether, butyl glycidyl ether, benzyl including but not limited to molecular backbone and contracts
Water glycerin ether, butanediol diglycidyl ether, 1,6 hexanediol diglycidylether, 1,2- cylohexanediol diglycidyl ether,
Polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, benzyl alcohol, benzyl carbinol, nonyl phenol, propene carbonate, three
Hydroxymethyl-propane triacrylate, diisopropanol methyl ether, toluene and dimethylbenzene etc. it is one or more, more preferable butyl shrinks sweet
Oily ether.
In component A of the present invention defoaming agent be one of polyacrylate and dimethyl silicone polymer or a variety of, it is excellent
Select one of BYK066N, BYKA530, BYK141 and BYK354 of Bi Ke chemistry or a variety of.
Epoxy hardener in B component of the present invention is mercaptan modified titanate esters phenolic aldehyde amine curable epoxide of the invention
Agent.
Coupling agent described in B component of the present invention is selected from 3- aminopropyl triethoxysilane (KH-550) and γ-metering system
One or both of acryloxypropylethoxysilane trimethoxy silane (KH-570), preferably KH-550.
The preparation method of component A of the present invention, comprising the following steps: mix epoxy resin, diluent and defoaming agent
It closes, is warming up to 50~75 DEG C, stir 2~4 hours, be uniformly mixed, stand.
The preparation method of B component of the present invention, comprising the following steps: epoxy hardener and coupling agent are mixed, risen
Temperature stirs 1~4h, uniformly rear standing to be mixed to 25~40 DEG C.
In the present invention, the phenolic aldehyde amine containing sulfydryl is prepared for using Mannich reaction, is synthesized by sulfydryl with titanium chloride class
Modified titanate esters curing agent, the curing agent have lower reactivity and blending viscosity at normal temperature, can satisfy large size
The requirement of casting construction process, after it is with epoxy resin mixed construction, under the action of atmospheric moisture, sulfydryl can be released
Come, by hydrogen bond-sulfydryl-phenolic hydroxyl group-tertiary amine synergistic effect, changes curable epoxide course, reactivity with higher,
It can be adapted for -25 DEG C of environment below.
Illustrate to prepare the epoxy by taking 2 mercapto ethanol, paraformaldehyde, P-hydroxybenzoic acid and WANALINK6200 as an example
The reaction process of curing agent:
The preparation method of composition epoxy resin of the present invention, comprising the following steps: by mass ratio be (3~8): 1,
It is preferred that (3.5~7): 1 component A is uniformly mixed with B component, deaeration, is solidified in carrier or mold.
Composition epoxy resin of the present invention can be used as concrete repair paint, specifically can be applied to harbour coagulation
Soil, concrete steel building, canal liner, pipe seal, bridge reparation, old workshop beam column defect reinforcement, cement column cap
The environment such as the humidity low temperature such as spreading, municipal works and large hydraulic engineering.
The beneficial effects of the present invention are:
(1) Mannich reaction, system are carried out by using aminated compounds, aldehyde compound and sulfhydrylation phenolic compound
The standby phenolic aldehyde amine containing sulfydryl, sulfydryl, tertiary amine and phenolic hydroxyl group present in the molecular structure have collaboration facilitation, can be with
In -25 DEG C or less cured epoxy resins, there is good caking property to concrete material；
(2) to solve the problems, such as to solidify in moist substrate surface, by the pnenolic aldehyde amine hardener and titanium chloride class of sulfydryl sealing end
It is reacted, is prepared for modified titanate ester curing agent, had both solved the problems, such as that the smell of mercaptan compound itself was larger, while
Sealing end protection is carried out to sulfydryl, epoxy hardener prepared by the present invention has lower reactivity at room temperature and mixes
Viscosity is closed, the use of bridge repairing encapsulating is particularly suitable for；
(3) after epoxy hardener of the invention is mixed with epoxy resin, under moisture effect, sulfydryl can be released, and be led to
Hydrogen bond-sulfydryl-phenolic hydroxyl group-tertiary amine synergistic effect is crossed, curable epoxide course is changed, so that mixed system is in 10~30min
It just shows intensity, is fully cured within 7 days at room temperature, and hydrolyze the titanate esters generated to increase substantially the attachment of epoxy coating
Power, impact strength and toughness；
(4) preparation process of the curing agent is simple, practical, obtained curing agent have the longer operating time and compared with
High curing activity solves -15 DEG C of presence or less solidifications difficulties, the gas such as polymercaptan, thiocarbamide polyamines and its imidazole derivative
The problem of taste threshold value is low, the operating time is short, can not be as the use of concrete repair paint.
Specific embodiment
By specific embodiment, the present invention will be further described, and embodiment of the present invention is intended only as to of the invention
Illustrate, does not limit the scope of the invention.
See Table 1 for details for raw material and source.
1 raw material of table and source
| Chemical name | Producer |
| WANLINK6200 | Wanhua Chemical Group Co., Ltd. |
| UNILINK4100 | US Air gasification chemical product Co., Ltd |
| UNLINK4102 | US Air gasification chemical product Co., Ltd |
| UNLINK7100 | US Air gasification chemical product Co., Ltd |
| P-hydroxybenzoic acid | Zhejiang Lv Sen Chemical Co., Ltd. |
| M-hydroxybenzoic acid | Nanjing chemical reagent limited liability company |
| 2 mercapto ethanol | Guangzhou Su Nuo Chemical Co., Ltd. |
| 3- sulfydryl -1- propyl alcohol | Guangdong Weng Jiang chemical reagent Co., Ltd |
| 37% formaldehyde | Jinan Chen Fu Chemical Co., Ltd. |
| (CH2O) n, n are 10~100 | Traditional Chinese medicines chemical reagent Co., Ltd |
| Glacial acetic acid | Jinan Jin Baihe Trade Co., Ltd. |
| Titanium tetrachloride | Nanjing chemical reagent limited liability company |
| Titanium trichloride | Nanjing chemical reagent limited liability company |
| KH-550 | Guangzhou Zhong Jie Chemical Industry Science Co., Ltd |
| KH-570 | Guangzhou Zhong Jie Chemical Industry Science Co., Ltd |
| Epoxy resin E51 (DER 331) | Dow Chemical |
| 1,4- butanediol diglycidyl ether (XY622) | New far Chemical Industry Co., Ltd. of Anhui |
| 1,6 hexanediol diglycidylether (XY632) | New far Chemical Industry Co., Ltd. of Anhui |
Compression strength: it is tested according to ISO 604；
Flexural strength: it is tested according to ISO 178；
Shore hardness: it is tested according to ASTM D2240, film thickness 2mm；
Embodiment 1
(1) preparation of epoxy hardener
1. 1mol m-hydroxybenzoic acid is uniformly mixed with 1.02mol2- mercaptoethanol, 165 DEG C are heated to, after reacting 3h
Moisture is removed, m-hydroxybenzoic acid mercapto ethyl ester is obtained；
2. under the catalytic action of 0.02mol% (amount ratio of acidic catalyst and aminated compounds, similarly hereinafter) glacial acetic acid,
2molWANALINK6200,1mol m-hydroxybenzoic acid mercapto ethyl ester and 1mol37% formaldehyde are uniformly mixed, are warming up to 90 DEG C,
9h is reacted, room temperature is then cooled to, obtains sulfhydrylation phenolic aldehyde amine.
3. 1mol titanium tetrachloride is added in 0.1mol benzene under agitation, be cooled to after addition 15 DEG C with
Under, it is passed through ammonia, the pH value to reaction system reaches 9, is slowly added to 2. sulfhydrylation phenolic aldehyde amine that 4mol is prepared, is warming up to 55
DEG C, 3.5h is reacted, collecting absolute pressure after reaction is 0.09MPa, and the fraction that temperature is 130 DEG C obtains ring of the present invention
Oxygen curing agent.
(2) preparation of composition epoxy resin
The preparation of component A: 70g DER331 is added in mixing apparatus, is warming up to 55 DEG C and is kept constant temperature；15g is added
XY622 and 15g BYKA530,70 DEG C are persistently stirred 2.5 hours, are uniformly mixed, and are stood；
The preparation of B component: the epoxy hardener and 15g KH-550 that prepare in 85g (1) are added in reaction kettle, make to react
The temperature of kettle is maintained at 25 DEG C, is sufficiently stirred 4 hours, is fitted into product container after mixing, seals room temperature preservation；
Resulting two component of AB is removed into bubble according to mass ratio for 3.5:1 after mixing, is 70% in humidity, temperature
It is to solidify to obtain composition epoxy resin for 24 hours at -15 DEG C, the shore hardness D of gained composition epoxy resin is 78, and compression strength is
112MPa, flexural strength 135MPa, application of the composition epoxy resin of the present invention on the concrete repair of harbour.
Embodiment 2
(1) preparation of epoxy hardener
1. 1mol P-hydroxybenzoic acid is uniformly mixed with 1.04mol3- sulfydryl -1- propyl alcohol, 175 DEG C are heated to, reaction
Moisture is removed after 3.5h, obtains m-hydroxybenzoic acid sulfydryl propyl ester；
2. under the catalytic action of 0.1mol%37% hydrochloric acid, by 1molUNLINK4100,3mol m-hydroxybenzoic acid mercapto
Base propyl ester and 6mol paraformaldehyde are uniformly mixed, and are warming up to 115 DEG C, are reacted 14h, are then cooled to room temperature, obtain sulfhydrylation phenolic aldehyde
Amine.
3. 1mol titanium trichloride is added in 0.5mol benzene under agitation, be cooled to after addition 15 DEG C with
Under, it is passed through ammonia, the pH value to reaction system reaches 10, is slowly added to 2. sulfhydrylation phenolic aldehyde amine that 3mol is prepared, is warming up to 85
DEG C, 6h is reacted, collecting absolute pressure after reaction is 0.1MPa, and it is solid to obtain epoxy of the present invention for the fraction that temperature is 140 DEG C
Agent.
(2) preparation of composition epoxy resin
The preparation of component A: 78g DER331 is added in mixing apparatus, is warming up to 55 DEG C and is kept constant temperature；10g is added
XY622 and 12g BYKA530,70 DEG C are persistently stirred 2.5 hours, are uniformly mixed, and are stood；
The preparation of B component: the epoxy hardener and 3g KH-550 that prepare in 97g (1) are added in reaction kettle, make to react
The temperature of kettle is maintained at 40 DEG C, is sufficiently stirred 2 hours, is fitted into product container after mixing, seals room temperature preservation；
Resulting two component of AB is removed into bubble according to mass ratio for 7:1 after mixing, is 75% in humidity, temperature
It is to solidify to obtain composition epoxy resin for 24 hours at -12 DEG C, the shore hardness D of gained composition epoxy resin is 80, and compression strength is
117MPa, flexural strength 133MPa, application of the composition epoxy resin of the present invention in bridge repairing.
Embodiment 3
(1) preparation of epoxy hardener
1. 1mol P-hydroxybenzoic acid is uniformly mixed with 1.03mol2- mercaptoethanol, 170 DEG C are heated to, reacts 3.2h
After remove moisture, obtain P-hydroxybenzoic acid mercapto ethyl ester；
2. under the catalytic action of 0.05mol%37% hydrochloric acid, by 1molUNLINK4102,2mol P-hydroxybenzoic acid mercapto
Base ethyl ester and 3mol paraformaldehyde are uniformly mixed, and are warming up to 100 DEG C, are reacted 12h, are then cooled to room temperature, obtain sulfhydrylation phenolic aldehyde
Amine.
3. 1mol titanium tetrachloride is added in 0.25mol benzene under agitation, be cooled to after addition 15 DEG C with
Under, it is passed through ammonia, the pH value to reaction system reaches 10, is slowly added to 2. sulfhydrylation phenolic aldehyde amine that 4mol is prepared, is warming up to 70
DEG C, 5h is reacted, collecting absolute pressure after reaction is 0.1MPa, and it is solid to obtain epoxy of the present invention for the fraction that temperature is 135 DEG C
Agent.
(2) preparation of composition epoxy resin
The preparation of component A: 75g DER331 is added in mixing apparatus, is warming up to 55 DEG C and is kept constant temperature；12g is added
XY632 and 10g BYK141,60 DEG C are persistently stirred 3 hours, are uniformly mixed, and are stood；
The preparation of B component: the epoxy hardener and 10g KH-570 that prepare in 90g (1) are added in reaction kettle, make to react
The temperature of kettle is maintained at 30 DEG C, is sufficiently stirred 1.5 hours, is fitted into product container after mixing, seals room temperature preservation；
Resulting two component of AB is uniformly mixed according to mass ratio for 4:1, is 90% in humidity, temperature is solid at -20 DEG C
Change and obtain composition epoxy resin for 24 hours, the shore hardness D of gained composition epoxy resin is 75, compression strength 102MPa, flexure
Intensity is 115MPa, application of the composition epoxy resin of the present invention on large hydraulic engineering.
Embodiment 4
(1) preparation of epoxy hardener
1. 1mol P-hydroxybenzoic acid is uniformly mixed with 1.04mol3- sulfydryl -1- propyl alcohol, 165 DEG C are heated to, reaction
Moisture is removed after 3.5h, obtains P-hydroxybenzoic acid sulfydryl propyl ester；
2. under the catalytic action of 0.05mol% glacial acetic acid, by 2molUNLINK4102,1mol P-hydroxybenzoic acid sulfydryl
Propyl ester and 12mol paraformaldehyde are uniformly mixed, and are warming up to 90 DEG C, are reacted 14h, are then cooled to room temperature, obtain sulfhydrylation phenolic aldehyde amine.
3. 1mol titanium trichloride is added in 0.35mol benzene under agitation, be cooled to after addition 15 DEG C with
Under, it is passed through ammonia, the pH value to reaction system reaches 9, and the slow sulfhydrylation phenolic aldehyde amine that 3mol is added and 2. prepares is warming up to 55 DEG C,
6h is reacted, collecting absolute pressure after reaction is 0.09MPa, and the fraction that temperature is 140 DEG C obtains curable epoxide of the present invention
Agent.
(2) preparation of composition epoxy resin
The preparation of component A: 70g DER331 is added in mixing apparatus, is warming up to 55 DEG C and is kept constant temperature；15g is added
XY632 and 10g BYK141,50 DEG C are persistently stirred 4 hours, are uniformly mixed, and are stood；
The preparation of B component: the epoxy hardener and 8g KH-570 that prepare in 92g (1) are added in reaction kettle, make to react
The temperature of kettle is maintained at 25 DEG C, is sufficiently stirred 4 hours, is fitted into product container after mixing, seals room temperature preservation；
Resulting two component of AB is removed into bubble according to mass ratio for 5:1 after mixing, is 65% in humidity, temperature
It is to solidify to obtain composition epoxy resin for 24 hours at -15 DEG C, the shore hardness D of gained composition epoxy resin is 78, and compression strength is
125MPa, flexural strength 130MPa, application of the composition epoxy resin of the present invention in pipe seal.
Embodiment 5
(1) preparation of epoxy hardener
1. 1mol P-hydroxybenzoic acid is uniformly mixed with 1.02mol2- mercaptoethanol, 175 DEG C are heated to, after reacting 3h
Moisture is removed, P-hydroxybenzoic acid mercapto ethyl ester is obtained；
2. under the catalytic action of 0.05mol% glacial acetic acid, by 2molUNLINK7100,6mol P-hydroxybenzoic acid sulfydryl
Ethyl ester and 1mol paraformaldehyde are uniformly mixed, and are warming up to 115 DEG C, are reacted 9h, are then cooled to room temperature, obtain sulfhydrylation phenolic aldehyde amine.
3. 1mol titanium tetrachloride is added in 0.4mol benzene under agitation, be cooled to after addition 15 DEG C with
Under, it is passed through ammonia, the pH value to reaction system reaches 10, is slowly added to 2. sulfhydrylation phenolic aldehyde amine that 4mol is prepared, is warming up to 85
DEG C, 3.5h is reacted, collecting absolute pressure after reaction is 0.1MPa, and the fraction that temperature is 130 DEG C obtains epoxy of the present invention
Curing agent.
(2) preparation of composition epoxy resin
The preparation of component A: 78g DER331 is added in mixing apparatus, is warming up to 55 DEG C and is kept constant temperature；11g is added
XY632 and 9g BYK141,75 DEG C are persistently stirred 2 hours, are uniformly mixed, and are stood；
The preparation of B component: the epoxy hardener and 9g KH-550 that prepare in 91g (1) are added in reaction kettle, make to react
The temperature of kettle is maintained at 25 DEG C, is sufficiently stirred 4 hours, is fitted into product container after mixing, seals room temperature preservation；
Resulting two component of AB is removed into bubble according to mass ratio for 6:1 after mixing, is 73% in humidity, temperature
It is to solidify to obtain composition epoxy resin for 24 hours at -25 DEG C, the shore hardness D of gained composition epoxy resin is 75, and compression strength is
98MPa, flexural strength 101MPa, application of the composition epoxy resin of the present invention on canal liner.
Comparative example
(1) preparation of epoxy hardener
1. 1mol P-hydroxybenzoic acid is uniformly mixed with 1.03mol2- mercaptoethanol, 175 DEG C are heated to, after reacting 3h
Moisture is removed, P-hydroxybenzoic acid mercapto ethyl ester is obtained；
2. under the catalytic action of 0.05mol% glacial acetic acid, by 1molWANALINK6200,3mol P-hydroxybenzoic acid mercapto
Base ethyl ester and 6mol paraformaldehyde are uniformly mixed, and are warming up to 100 DEG C, are reacted 12h, are then cooled to room temperature, obtain sulfhydrylation phenolic aldehyde
Amine.
(2) preparation of composition epoxy resin
The preparation of component A: 78g DER 331 is added in mixing apparatus, is warming up to 55 DEG C and is kept constant temperature；It is added
11g XY632 and 9g BYK141,75 DEG C are persistently stirred 2 hours, are uniformly mixed, and are stood；
The preparation of B component: the sulfhydrylation phenolic aldehyde amine and 10g KH-550 that prepare in 90g (1) are added in reaction kettle, are made anti-
It answers the temperature of kettle to be maintained at 25 DEG C, is sufficiently stirred 4 hours, is fitted into product container after mixing, seal room temperature preservation；
Resulting two component of AB is removed into bubble according to mass ratio for 4:1 after mixing, is 73% in humidity, temperature
It is to solidify to obtain composition epoxy resin for 24 hours at -25 DEG C, the shore hardness D of gained composition epoxy resin is 45, and compression strength is
51MPa, flexural strength 70MPa.
Claims (22)
1. a kind of epoxy hardener, structural formula are as follows:
Wherein, R1It representsAnd R1From P-hydroxybenzoic acid or m-hydroxybenzoic acid, R2Representative-CH2-
CH2-、-CH2-CH2-CH2-、-CH2-CH2-CH2-CH2OrR3It represents R4It represents N is 1 or 10~100, m
It is 3 or 4.
2. a kind of method for preparing epoxy hardener described in claim 1, comprising the following steps:
1) phenolic compound containing carboxyl is reacted to obtain to sulfhydrylation phenolic compound with mercaptan compound；
2) under the action of acidic catalyst, aminated compounds, sulfhydrylation phenolic compound and aldehyde compound are uniformly mixed,
React to obtain sulfydryl sealing end phenolic aldehyde amine；
3) it is passed through ammonia into the mixture of chlorination titanium compound and benzene, the pH value to reaction system reaches 9~10, slowly adds
Enter sulfydryl sealing end phenolic aldehyde amine, distillation obtains epoxy hardener after reaction.
3. according to the method described in claim 2, it is characterized in that, in step 1), phenolic compound and mercaptan containing carboxyl
The molar ratio of compound is 1:1.01~1.05.
4. according to the method described in claim 3, it is characterized in that, in step 1), phenolic compound and mercaptan containing carboxyl
The molar ratio of compound is 1:1.02~1.04.
5. according to the method described in claim 2, it is characterized in that, in step 1), the phenolic compound containing carboxyl be between hydroxyl
Yl benzoic acid and/or P-hydroxybenzoic acid；Mercaptan compound is selected from 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 4- sulfydryl -1- fourth
One of pure and mild 2- sulfydryl -3- butanol is a variety of.
6. according to the method described in claim 2, reaction temperature is 160~180 DEG C it is characterized in that, in step 1), when reaction
Between be 2~5h.
7. according to the method described in claim 6, reaction temperature is 165~175 DEG C it is characterized in that, in step 1), when reaction
Between be 3~3.5h.
8. according to the method described in claim 2, it is characterized in that, in step 2), aminated compounds, sulfhydrylation phenolic compound
Molar ratio with aldehyde compound is 1:0.5~3:0.5~6.
9. according to the method described in claim 8, it is characterized in that, in step 2), aminated compounds, sulfhydrylation phenolic compound
Molar ratio with aldehyde compound is 1:0.6~2.7:0.6~5.5.
10. according to the method described in claim 2, it is characterized in that, aminated compounds described in step 2) is that aromatic series is double secondary
Amine, UNILINK7100, UNILINK4100 and UNILINK4102 of WANALINK6200, air chemical industry selected from ten thousand China's chemistry
One of or it is a variety of；
The aldehyde compound is the formalin and/or paraformaldehyde of 35wt%~40wt%.
11. according to the method described in claim 2, it is characterized in that, in step 2), the acidic catalyst be selected from acetic acid,
The hydrochloride of hydrochloric acid and amine；
The dosage of the acidic catalyst is 0.01mol%~0.1mol% of aminated compounds.
12. according to the method described in claim 2, reaction temperature is 80~120 DEG C it is characterized in that, in step 2), when reaction
Between be 7~15h.
13. according to the method for claim 12, which is characterized in that in step 2), reaction temperature is 90~115 DEG C, reaction
Time is 9~14h.
14. according to the method described in claim 2, it is characterized in that, the chlorination titanium compound is trichlorine in step 3)
Change titanium and/or titanium tetrachloride；
The molar ratio of the chlorination titanium compound and sulfydryl sealing end phenolic aldehyde amine is 1:3~4.05.
15. according to the method described in claim 2, reaction temperature is 40~90 DEG C it is characterized in that, in step 3), when reaction
Between be 3~7h.
16. according to the method for claim 15, which is characterized in that in step 3), reaction temperature is 55~85 DEG C, when reaction
Between be 3.5~6h.
17. a kind of composition epoxy resin, including component A and B component；
Wherein the component A includes: it is based on component A weight,
60.0~80wt% of epoxy resin；
2~20wt% of diluent；
1~20wt% of defoaming agent；
The B component includes: it is based on B component weight,
85~97wt% of epoxy hardener
3~15wt% of coupling agent
The epoxy hardener is for epoxy hardener described in claim 1 or according to any one of claim 2-16 the method
The epoxy hardener of preparation.
18. composition epoxy resin according to claim 17, which is characterized in that wherein the component A includes: being based on A
Composition weight,
70~78wt% of epoxy resin；
7~15wt% of diluent；
8~15wt% of defoaming agent.
19. composition epoxy resin described in 7 or 18 according to claim 1, which is characterized in that the matter of the component A and B component
Amount is than being 3~8:1.
20. composition epoxy resin according to claim 19, which is characterized in that the mass ratio of the component A and B component
For 3.5~7:1.
21. a kind of method for preparing the described in any item composition epoxy resins of claim 17-20, comprising the following steps:
(1) epoxy resin, diluent and defoaming agent are mixed, is warming up to 50~75 DEG C, be uniformly mixed, standing obtains component A；
(2) epoxy hardener and coupling agent are mixed, is warming up to 25~40 DEG C, stood obtain B component after mixing；
(3) component A is uniformly mixed with B component, deaeration, solidification obtains the epoxy composite in carrier or mold
Object.
22. the preparation of method described in the described in any item composition epoxy resins of 7-20 or claim 21 according to claim 1
Composition epoxy resin purposes, which is characterized in that the composition epoxy resin be used for concrete repair paint.
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| CN201711019516.0A CN107722241B (en) | 2017-10-27 | 2017-10-27 | A kind of epoxy hardener and its preparation method and application |
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| CN201711019516.0A CN107722241B (en) | 2017-10-27 | 2017-10-27 | A kind of epoxy hardener and its preparation method and application |
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| CN110358057B (en) * | 2019-07-24 | 2020-08-18 | 海洋化工研究院有限公司 | Water-based epoxy resin curing agent and preparation method thereof |
| CN112608700B (en) * | 2020-11-30 | 2022-08-02 | 江阴职业技术学院 | Epoxy adhesive for cutting photovoltaic silicon wafer and preparation method thereof |
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| CN102443139A (en) * | 2011-09-22 | 2012-05-09 | 福建省东协橡塑实业有限公司 | Polymercaptan curing agent and preparation method thereof |
| CN103865037A (en) * | 2014-04-01 | 2014-06-18 | 山东圣泉化工股份有限公司 | Phenolic aldehyde amine curing agent and preparation method thereof |
| CN106995527A (en) * | 2017-05-19 | 2017-08-01 | 江苏三木化工股份有限公司 | A kind of composite epoxy curing agent and preparation method for anticorrosive paint |
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| CN102443139A (en) * | 2011-09-22 | 2012-05-09 | 福建省东协橡塑实业有限公司 | Polymercaptan curing agent and preparation method thereof |
| CN103865037A (en) * | 2014-04-01 | 2014-06-18 | 山东圣泉化工股份有限公司 | Phenolic aldehyde amine curing agent and preparation method thereof |
| CN106995527A (en) * | 2017-05-19 | 2017-08-01 | 江苏三木化工股份有限公司 | A kind of composite epoxy curing agent and preparation method for anticorrosive paint |
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